US9533328B2 - Clear coating composition and method for coating automobile body - Google Patents
Clear coating composition and method for coating automobile body Download PDFInfo
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- US9533328B2 US9533328B2 US14/130,455 US201214130455A US9533328B2 US 9533328 B2 US9533328 B2 US 9533328B2 US 201214130455 A US201214130455 A US 201214130455A US 9533328 B2 US9533328 B2 US 9533328B2
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- coating film
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- 238000000576 coating method Methods 0.000 title claims abstract description 232
- 239000011248 coating agent Substances 0.000 title claims abstract description 230
- 239000008199 coating composition Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 claims abstract description 92
- 239000011347 resin Substances 0.000 claims abstract description 92
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 85
- 239000004640 Melamine resin Substances 0.000 claims abstract description 66
- 239000012948 isocyanate Substances 0.000 claims abstract description 64
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 60
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 49
- 239000010959 steel Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- -1 acrylic polyol Chemical class 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract 5
- 239000007788 liquid Substances 0.000 claims description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 21
- 238000004070 electrodeposition Methods 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000005452 bending Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 6
- 238000001723 curing Methods 0.000 description 45
- 239000002253 acid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002987 primer (paints) Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
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- 239000002981 blocking agent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000002250 progressing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
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- 239000013638 trimer Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Definitions
- the present invention relates to a clear coating composition and a method for coating an automobile body.
- automobile bodies are configured from a portion formed by resin components such as bumpers (hereinafter referred to as “resin part”), and a portion formed by steel sheet components such as the body (hereinafter referred to as “steel sheet part”).
- resin part a portion formed by resin components such as bumpers
- steel sheet part a portion formed by steel sheet components such as the body
- a technology for coating a water-based base coating containing melamine resin and emulsion resin obtained by emulsion polymerizing an ethylenically unsaturated monomer mixture containing methacrylic acid ester, and then coating wet-on-wet a clear coating with isocyanate as a curing agent (refer to Patent Document 1).
- this technology it is said to be possible to form a coating film superior in low-temperature curability and well as being superior in adhesiveness, even in a case of simultaneously coating both parts among the resin part and steel sheet part.
- a low-temperature curing coating for example, a clear coating for automobile bodies containing predetermined amounts of acrylic polyol, blocked isocyanate and melamine resin (refer to Patent Document 2), a top-coat coating for automobile bodies containing predetermined amounts of acrylic polyol, alkoxysilane and blocked isocyanate and melamine resin (refer to Patent Document 3), a water-based heat curable coating for automobile bodies containing predetermined amounts of acrylic polyol, blocked isocyanate and melamine resin (refer to Patent Document 4), etc. have been proposed.
- Patent Document 1 Japanese Unexamined Patent Application, Publication No. 2005-787
- Patent Document 2 Japanese Unexamined Patent Application, Publication No. H10-101995
- Patent Document 3 Japanese Unexamined Patent Application, Publication No. H10-88010
- Patent Document 4 Japanese Unexamined Patent Application, Publication No. 2001-139879
- the coating film formed simultaneously on both parts among resin part and steel sheet part has been insufficient in bending resistance. For this reason, the durability of the coating film has been inadequate, and thus defects such as cracking may occur.
- the present invention has been made taking the above into account, and the object thereof is to provide a coating composition that simultaneously form a coating film on both parts among resin part and steel sheet part at lower temperature than conventionally, as well as being able to form a coating film having superior bending resistance.
- a clear coating composition according to the present invention includes: a base resin containing acrylic polyol; a crosslinking agent consisting of an active methylene-type blocked isocyanate and melamine resin; and a curing catalyst, in which a mass ratio of the base resin to the melamine resin is 1.5 to 9.0, and when defining a total of mass percentage of the base resin and mass percentage of the melamine resin in the composition as 100% by mass, the minimum value for mass percentage of the active methylene-type blocked isocyanate in the composition is calculated according to formula (1) below, and the maximum value thereof is calculated according to formula (2) below.
- the clear coating composition is configured to contain the base resin containing acrylic polyol, the crosslinking agent consisting of active methylene-type blocked isocyanate and melamine resin, and the curing catalyst.
- the mass ratio of the base resin relative to the melamine resin is set to within the range of 1.5 to 9.0.
- an active methylene-type blocked isocyanate having a property of curing at low temperature in addition to the melamine resin, it is possible to bake to cure at a lower temperature than conventionally, e.g., a low temperature of 90° C. to 120° C. For this reason, for example, even without using heat resistant resin components (e.g., resin components blending glass filler), simultaneous coating is possible on both parts among the resin part and the steel sheet part of an automobile body, and thus it is possible to avoid deviation in hue occurring when coating each respective part.
- heat resistant resin components e.g., resin components blending glass filler
- the minimum value for the mass percentage of the active methylene-type blocked isocyanate in the composition is defined as a value calculated according to the aforementioned formula (1), and the maximum value is defined as a value calculated according to the aforementioned formula (2), when the total of the mass percentage of the base resin and the mass percentage of the melamine resin in the composition is defined as 100% by mass.
- the cured product has a hard characteristic due to the melamine resin and base resin; whereas, the cured product of the blocked isocyanate and base resin has a soft characteristic. Therefore, according to the present invention, it is possible to appropriately control the elasticity of the coating film, by setting the mass percentage of the active methylene-type blocked isocyanate in the composition to within a specific range. More specifically, by defining the mass percentage of the active methylene-type blocked isocyanate in the composition as at least the above-mentioned minimum value, it is possible to make the coating film overall a flexible film while maintaining a fixed coating film hardness due to imparting of elasticity according to the cured product of blocked isocyanate and base resin, and a coating film having superior bending resistance is obtained.
- the mass percentage of the active methylene-type blocked isocyanate in the composition as no more than the above-mentioned maximum value, it is possible to avoid the coating film from excessively softening and the permeability increasing, and thus it is possible to avoid declines in stain resistance and acid resistance.
- the curing catalyst prefferably contains dibutyltin dilaurate as a blocked isocyanate curing catalyst, and p-toluene sulfonic acid as a melamine curing catalyst.
- the curing catalyst is configured to include dibutyltin dilaurate as the blocked isocyanate curing catalyst, and p-toluene sulfonic acid as the melamine curing catalyst.
- the curing catalyst prefferably contains a melamine curing catalyst
- the clear coating composition to be a two-part coating composition consisting of a first liquid and a second liquid, the melamine resin being contained in the first liquid, and the melamine curing catalyst being contained in the second liquid.
- the curing catalyst is configured to include a melamine curing catalyst.
- the clear coating composition is made as two-part type, with the melamine resin being contained in the first liquid, while the melamine curing catalyst is contained in the second liquid.
- a method for coating an automobile body includes: a base-coating coating step of simultaneously coating a base coating on both parts among a resin part and a steel sheet part of an automobile body to form a base coating film thereon; a clear-coating coating step of simultaneously coating a clear coating on both parts among the resin part and the steel sheet part on which the base coating film was formed to form a clear coating film thereon; and a curing step of baking the clear coating film to cure, in which the clear coating composition as described in any one of claims 1 to 3 is coated in the clear-coating coating step.
- the aforementioned clear coating composition is used in a method for coating that simultaneously coats a base coating on both parts among resin part and steel sheet part of an automobile body, and then simultaneously coating a clear coating and allowing to cure.
- the same effects as the invention of the aforementioned clear coating composition are exerted according to the present invention.
- the resin components are assembled to the electrocoated steel sheet components to construct the automobile body, and the base coating is coated on this. Moreover, subsequently, the clear coating is coated wet-on-wet, and the base coating film and clear coating film are simultaneously baked to cure.
- the coating film formed by wet-on-wet coating has a characteristic of being difficult to cure; however, since the clear coating composition according to the present invention excels in low-temperature curability, it is possible to cause the coating film to reliably cure even under low-temperature conditions, and thus a coating film can be formed that excels in bending resistance, stain resistance and acid resistance. In other words, the clear coating composition according to the present invention is suited to wet-on-wet coating.
- the present invention it is possible to provide a coating composition that can form a coating film simultaneously on both parts among a resin part and a steel sheet part at lower temperature than conventionally, as well as being able to form a coating film having superior bending resistance.
- FIG. 1 is a graph showing a relationship between the mass ratio of base resin to melamine resin, and the mass percentage of active methylene-type blocked isocyanate in the composition, when defining the total of mass percentage of base resin and mass percentage of melamine resin in the composition as 100% by mass.
- a clear coating composition according to the embodiment of the present invention cures at lower temperature than conventionally; therefore, simultaneous coating on both parts among a resin part and a steel sheet part of an automobile body is possible.
- resin components forming the resin part are exterior components such as bumpers and resin fenders, for example, and steel sheet components forming the steel sheet part are the body, for example.
- the clear coating composition according to the present embodiment is a two-part clear coating composition consisting of a first liquid and a second liquid, and prior to coating, the first liquid and the second liquid are mixed, and then coated.
- the clear coating composition according to the present embodiment is configured to contain a base resin, a crosslinking agent and a curing catalyst.
- the base resin is configured to contain an acrylic polyol.
- an acrylic polyol having an OHV (hydroxyl value) of 80 to 200 KOH mg/g can be preferably used.
- the acrylic polyol causes the coating film to cure by a crosslinking reaction of the hydroxyl group thereof with a melamine resin or active methylene-type blocked isocyanate described later.
- the crosslinking agent is configured from a melamine resin and an active methylene-type blocked isocyanate.
- a commercial product can be used as the melamine resin.
- a melamine resin having a high degree of alkylation e.g., hexamethoxy methylated melamine resin “CYMEL (registered trademark) 300” manufactured by Nihon Cytec Industries Inc., is used. Due to having high reactivity, the melamine resin with a high degree of alkylation causes the coating film to cure at lower temperature by the crosslinking reaction progressing.
- a commercial product can be used as the active methylene-type blocked isocyanate.
- blocked isocyanate is an isocyanate compound in which a free isocyanate group is blocked by a blocking agent.
- the blocked isocyanate causes the coating film to cure by the blocking agent dissociating and the isocyanate group regenerating due to heating, and then a crosslinking reaction with the hydroxy group of the acrylic polyol. At this time, a urethane bond is formed by the crosslinking reaction between the isocyanate and acrylic polyol.
- active methylene-type blocked isocyanate indicates an isocyanate compound blocked by an active methylene-type blocking agent having an active methylene group.
- the active methylene-type blocking agent has a characteristic of dissociating at lower temperature; therefore, the active methylene-type blocked isocyanate causes the coating film to cure by the crosslinking reaction progressing at lower temperature.
- active methylene-type blocking agent for example, dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, acetylacetone, etc. can be used.
- the isocyanate compound is configured from a monomer, dimer and trimer.
- the main components of the isocyanate compound are the dimer uretodione structure and trimer isocyanurate structure, and these account for about 99.5% thereof.
- the monomer constituting the remaining about 0.5% is said to have high toxicity to organisms; however, according to a blocked isocyanate in which the isocyanate group is blocked by a blocking agent, the high toxicity thereof is avoided.
- the curing catalyst is configured to contain a melamine curing catalyst and a blocked isocyanate curing catalyst.
- strong acid catalysts such as an organic sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid and p-toluene sulfonic acid are used preferably.
- dibutyltin dilaurate DBTDL
- dibutyltin bis-o-phenylphenate dibutyltin marate
- dibutyltin diacetate dibutyltin diacetate
- dibutyltin dilaurylmercaptide dimethyltin dichloride, etc.
- the melamine curing catalyst is contained in a different liquid from the liquid in which the melamine resin is contained. More specifically, in the case of the melamine resin being contained in the first liquid, the melamine curing catalyst will be contained in the second liquid. The melamine resin thereby will not react with the base resin and cure prior to coating.
- each of the other components may be contained in either of the first liquid and the second liquid.
- all components other than the melamine curing catalyst may be contained in the first liquid, and only the melamine curing catalyst contained in the second liquid.
- the coating film cures at lower temperature than conventionally, as well as a coating film being obtained having superior bending resistance while maintaining a constant coating film hardness.
- the minimum value for the mass percentage of the active methylene-type blocked isocyanate in the composition is calculated according to the following formula (1), and the maximum value is calculated by the following formula (2), when the total of the mass percentage of base resin and the mass percentage of melamine resin in the composition is defined as 100% by mass.
- the mass percentage of the active methylene-type blocked isocyanate in the composition being at least the above-mentioned minimum value, it is possible to make the coating film overall a flexible film while maintaining a certain coating film hardness due to imparting of elasticity according to the cured product of blocked isocyanate and base resin, and a coating film having superior bending resistance is obtained.
- the mass percentage of the active methylene-type blocked isocyanate in the composition being no more than the above-mentioned maximum value, it is possible to avoid the coating film from excessively softening and the permeability increasing, and thus it is possible to avoid declines in stain resistance and acid resistance.
- the clear coating composition according to the present embodiment is not concerned with being an aqueous system or an organic solvent system.
- predetermined amounts of various additives and various solvents may be contained. It is not limited in regards to production method, and can be produced according to a conventional, well-known preparation method.
- the method for coating an automobile body according to the present embodiment includes a base-coating coating step, a clear-coating coating step, and a curing step.
- a base-coating film is formed by simultaneously coating the base coating on both parts among the resin part and steel sheet part of the automobile body.
- a conventional, well-known base coating can be used as the base coating.
- the method for coating an automobile body prior to the base-coating coating step, it preferably includes an electrocoating step of electrocoating steel sheet components forming the steel sheet part, and an assembly step of assembling the electrocoated steel sheet components and the resin components forming the resin part to make one set automobile body.
- the resin components are preferably applied a conductive primer, and then inserted in the step after the electrocoat drying of the steel sheet components. After insertion, the resin components and steel sheet components are assembled to make the automobile body, and then the base coating film and the clear coating film are sequentially coated wet-on-wet, followed by simultaneously baking to cure. However, the resin components are inserted in the step after intermediate-coat preheating of the steel sheet components, and intermediate-coat coating does not need to be performed for the resin components.
- the resin components are preferably applied a conductive primer, and then inserted in the step after the electrocoat drying of the steel sheet components. After insertion, the resin components and steel sheet components are assembled to make the automobile body, and then the base coating film (two-layer configuration) and the clear coating film are sequentially coated wet-on-wet, followed by simultaneously baking to cure.
- the clear coating composition is configured to contain the base resin containing acrylic polyol, the crosslinking agent consisting of active methylene-type blocked isocyanate and melamine resin, and the curing catalyst.
- the mass ratio of the base resin relative to the melamine resin is set to within the range of 1.5 to 9.0.
- the aforementioned clear coating composition is used in a method for coating that simultaneously coats a base coating on both parts among resin part and steel sheet part of an automobile body, and then simultaneously coating a clear coating and allowing to cure.
- the same effects as the invention of the aforementioned clear coating composition are thereby exerted.
- the resin components are assembled to the electrocoated steel sheet components to construct the automobile body, and the base coating is coated on this. Moreover, subsequently, the clear coating is coated wet-on-wet, and the base coating film and clear coating film are simultaneously baked to cure.
- the base coating film and clear coating film were formed and made to cure.
- FIG. 1 is a graph showing the relationships between the mass ratio of acrylic polyol relative to melamine resin (x axis), and mass percentage of active methylene-type blocked isocyanate in the composition when defining the total of the mass percentage of acrylic polyol and the mass percentage of melamine resin in the composition as 100% by mass (y axis), based on the blending of the clear coating compositions of Examples 1 to 15 shown in Table 1.
- R represents the acrylic polyol
- MF represents the melamine resin
- BI represents the active methylene-type blocked isocyanate.
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Abstract
To provide a coating composition, which is capable of providing a coating film on a resin part and on a steel plate part at the same time at lower temperatures than conventional coating compositions, and which is capable of providing a coating film that has excellent bending resistance. A clear coating composition, which contains a base material that contains an acrylic polyol, a crosslinking agent that is composed of an active methylene type blocked isocyanate and a melamine resin, and a curing catalyst. The mass ratio of the base material to the melamine resin is 1.5-9.0, and the mass percentage of the active methylene type blocked isocyanate in the composition is set within a specific range when the total of the mass percentage of the base material and the mass percentage of the melamine resin in the composition is taken as 100% by mass.
Description
The present invention relates to a clear coating composition and a method for coating an automobile body.
Normally, automobile bodies are configured from a portion formed by resin components such as bumpers (hereinafter referred to as “resin part”), and a portion formed by steel sheet components such as the body (hereinafter referred to as “steel sheet part”). Herein, there is concern over the resin part deforming when baking, in the case of coating a coating of high baking temperature onto the resin part, since the heat resistance of resin components are greatly inferior compared to steel sheet components. For this reason, it is common practice to coat a suitable coating at suitable coating conditions on every respective part.
However, when coating different coatings on every respective part, deviation in hue occurs, and appearance of the automobile may decline. Therefore, development of a coating that can simultaneously coat both parts among a resin part and a steel sheet part, and nevertheless be of low-temperature curing type has been demanded.
For example, a technology for coating a water-based base coating containing melamine resin and emulsion resin obtained by emulsion polymerizing an ethylenically unsaturated monomer mixture containing methacrylic acid ester, and then coating wet-on-wet a clear coating with isocyanate as a curing agent (refer to Patent Document 1). According to this technology, it is said to be possible to form a coating film superior in low-temperature curability and well as being superior in adhesiveness, even in a case of simultaneously coating both parts among the resin part and steel sheet part.
In addition, as a low-temperature curing coating, for example, a clear coating for automobile bodies containing predetermined amounts of acrylic polyol, blocked isocyanate and melamine resin (refer to Patent Document 2), a top-coat coating for automobile bodies containing predetermined amounts of acrylic polyol, alkoxysilane and blocked isocyanate and melamine resin (refer to Patent Document 3), a water-based heat curable coating for automobile bodies containing predetermined amounts of acrylic polyol, blocked isocyanate and melamine resin (refer to Patent Document 4), etc. have been proposed.
[Patent Document 1] Japanese Unexamined Patent Application, Publication No. 2005-787
[Patent Document 2] Japanese Unexamined Patent Application, Publication No. H10-101995
[Patent Document 3] Japanese Unexamined Patent Application, Publication No. H10-88010
[Patent Document 4] Japanese Unexamined Patent Application, Publication No. 2001-139879
However, from the viewpoint of a reduction in consumed energy and a reducing in CO2 emissions during coating film formation, further lowering of the temperature of the baking temperature has been demanded.
In addition, with the conventional technology, the coating film formed simultaneously on both parts among resin part and steel sheet part has been insufficient in bending resistance. For this reason, the durability of the coating film has been inadequate, and thus defects such as cracking may occur.
The present invention has been made taking the above into account, and the object thereof is to provide a coating composition that simultaneously form a coating film on both parts among resin part and steel sheet part at lower temperature than conventionally, as well as being able to form a coating film having superior bending resistance.
In order to achieve the above-mentioned object, the present invention provides a clear coating composition to be simultaneously coated on both parts among the resin part and steel sheet part of an automobile body. A clear coating composition according to the present invention includes: a base resin containing acrylic polyol; a crosslinking agent consisting of an active methylene-type blocked isocyanate and melamine resin; and a curing catalyst, in which a mass ratio of the base resin to the melamine resin is 1.5 to 9.0, and when defining a total of mass percentage of the base resin and mass percentage of the melamine resin in the composition as 100% by mass, the minimum value for mass percentage of the active methylene-type blocked isocyanate in the composition is calculated according to formula (1) below, and the maximum value thereof is calculated according to formula (2) below.
[Math. 1]
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74−×(mass ratio of base resin to melamine resin)+43.21 (2)
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74−×(mass ratio of base resin to melamine resin)+43.21 (2)
In the present invention, the clear coating composition is configured to contain the base resin containing acrylic polyol, the crosslinking agent consisting of active methylene-type blocked isocyanate and melamine resin, and the curing catalyst. In addition, the mass ratio of the base resin relative to the melamine resin is set to within the range of 1.5 to 9.0.
According to the present invention, by blending an active methylene-type blocked isocyanate having a property of curing at low temperature, in addition to the melamine resin, it is possible to bake to cure at a lower temperature than conventionally, e.g., a low temperature of 90° C. to 120° C. For this reason, for example, even without using heat resistant resin components (e.g., resin components blending glass filler), simultaneous coating is possible on both parts among the resin part and the steel sheet part of an automobile body, and thus it is possible to avoid deviation in hue occurring when coating each respective part.
In addition, with the present invention, the minimum value for the mass percentage of the active methylene-type blocked isocyanate in the composition is defined as a value calculated according to the aforementioned formula (1), and the maximum value is defined as a value calculated according to the aforementioned formula (2), when the total of the mass percentage of the base resin and the mass percentage of the melamine resin in the composition is defined as 100% by mass.
Herein, the cured product has a hard characteristic due to the melamine resin and base resin; whereas, the cured product of the blocked isocyanate and base resin has a soft characteristic. Therefore, according to the present invention, it is possible to appropriately control the elasticity of the coating film, by setting the mass percentage of the active methylene-type blocked isocyanate in the composition to within a specific range. More specifically, by defining the mass percentage of the active methylene-type blocked isocyanate in the composition as at least the above-mentioned minimum value, it is possible to make the coating film overall a flexible film while maintaining a fixed coating film hardness due to imparting of elasticity according to the cured product of blocked isocyanate and base resin, and a coating film having superior bending resistance is obtained. On the other hand, by defining the mass percentage of the active methylene-type blocked isocyanate in the composition as no more than the above-mentioned maximum value, it is possible to avoid the coating film from excessively softening and the permeability increasing, and thus it is possible to avoid declines in stain resistance and acid resistance.
It is preferable for the curing catalyst to contain dibutyltin dilaurate as a blocked isocyanate curing catalyst, and p-toluene sulfonic acid as a melamine curing catalyst.
In the present invention, the curing catalyst is configured to include dibutyltin dilaurate as the blocked isocyanate curing catalyst, and p-toluene sulfonic acid as the melamine curing catalyst.
It is thereby possible to cause the crosslinking reaction by the blocked isocyanate and the crosslinking reaction by the melamine resin to reliably progress, respectively, and more reliably cause the coating film to cure even under low-temperature conditions.
It is preferable for the curing catalyst to contain a melamine curing catalyst, and the clear coating composition to be a two-part coating composition consisting of a first liquid and a second liquid, the melamine resin being contained in the first liquid, and the melamine curing catalyst being contained in the second liquid.
In the present invention, the curing catalyst is configured to include a melamine curing catalyst. In addition, the clear coating composition is made as two-part type, with the melamine resin being contained in the first liquid, while the melamine curing catalyst is contained in the second liquid.
It is thereby possible to avoid the melamine resin having a characteristic of the crosslinking reaction progressing at low temperature from reacting with the base resin and curing prior to mixing the first liquid and second liquid, and then coating. In other words, a coating composition is obtained that excels in low-temperature curability during coating, while excelling in production engineerability.
In addition, A method for coating an automobile body includes: a base-coating coating step of simultaneously coating a base coating on both parts among a resin part and a steel sheet part of an automobile body to form a base coating film thereon; a clear-coating coating step of simultaneously coating a clear coating on both parts among the resin part and the steel sheet part on which the base coating film was formed to form a clear coating film thereon; and a curing step of baking the clear coating film to cure, in which the clear coating composition as described in any one of claims 1 to 3 is coated in the clear-coating coating step.
In the present invention, the aforementioned clear coating composition is used in a method for coating that simultaneously coats a base coating on both parts among resin part and steel sheet part of an automobile body, and then simultaneously coating a clear coating and allowing to cure. The same effects as the invention of the aforementioned clear coating composition are exerted according to the present invention.
It is preferable to further include: an electrocoating step of electrocoating a steel sheet component forming the steel sheet part, prior to the base-coating coating step; and an assembly step of assembling the steel sheet component thus electrocoated and a resin component forming the resin part so as to make a set of an automobile body, in which the clear coating is coated wet-on-wet in the clear-coating coating step, and the base coating film and the clear coating film are simultaneously baked to cure in the curing step.
In the present invention, the resin components are assembled to the electrocoated steel sheet components to construct the automobile body, and the base coating is coated on this. Moreover, subsequently, the clear coating is coated wet-on-wet, and the base coating film and clear coating film are simultaneously baked to cure.
Normally, the coating film formed by wet-on-wet coating has a characteristic of being difficult to cure; however, since the clear coating composition according to the present invention excels in low-temperature curability, it is possible to cause the coating film to reliably cure even under low-temperature conditions, and thus a coating film can be formed that excels in bending resistance, stain resistance and acid resistance. In other words, the clear coating composition according to the present invention is suited to wet-on-wet coating.
According to the present invention, it is possible to provide a coating composition that can form a coating film simultaneously on both parts among a resin part and a steel sheet part at lower temperature than conventionally, as well as being able to form a coating film having superior bending resistance.
Hereinafter, an embodiment of the present invention will be explained.
A clear coating composition according to the embodiment of the present invention cures at lower temperature than conventionally; therefore, simultaneous coating on both parts among a resin part and a steel sheet part of an automobile body is possible. Herein, resin components forming the resin part are exterior components such as bumpers and resin fenders, for example, and steel sheet components forming the steel sheet part are the body, for example.
The clear coating composition according to the present embodiment is a two-part clear coating composition consisting of a first liquid and a second liquid, and prior to coating, the first liquid and the second liquid are mixed, and then coated. The clear coating composition according to the present embodiment is configured to contain a base resin, a crosslinking agent and a curing catalyst.
The base resin is configured to contain an acrylic polyol. As the acrylic polyol, an acrylic polyol having an OHV (hydroxyl value) of 80 to 200 KOH mg/g can be preferably used.
The acrylic polyol causes the coating film to cure by a crosslinking reaction of the hydroxyl group thereof with a melamine resin or active methylene-type blocked isocyanate described later.
It should be noted that, by appropriately setting the glass transition temperature (Tg), molecular weight, acid value, etc. of the acrylic polyol, it is possible to form curable coating films having different physical properties.
The crosslinking agent is configured from a melamine resin and an active methylene-type blocked isocyanate.
A commercial product can be used as the melamine resin. Preferably, a melamine resin having a high degree of alkylation, e.g., hexamethoxy methylated melamine resin “CYMEL (registered trademark) 300” manufactured by Nihon Cytec Industries Inc., is used. Due to having high reactivity, the melamine resin with a high degree of alkylation causes the coating film to cure at lower temperature by the crosslinking reaction progressing.
It should be noted that, by appropriately setting the degree alkylation degree of the melamine resin, molecular weight, etc., it is possible to form cured coating films having different physical properties.
A commercial product can be used as the active methylene-type blocked isocyanate. For example, “Duranate (registered trademark) MF-K60X” manufactured by Asahi Kasei Chemicals Corp. in which 1,6-hexamethylene diisocyanate is blocked by an active methylene-type blocking agent is preferably used.
Herein, blocked isocyanate is an isocyanate compound in which a free isocyanate group is blocked by a blocking agent. The blocked isocyanate causes the coating film to cure by the blocking agent dissociating and the isocyanate group regenerating due to heating, and then a crosslinking reaction with the hydroxy group of the acrylic polyol. At this time, a urethane bond is formed by the crosslinking reaction between the isocyanate and acrylic polyol.
In addition, active methylene-type blocked isocyanate indicates an isocyanate compound blocked by an active methylene-type blocking agent having an active methylene group. The active methylene-type blocking agent has a characteristic of dissociating at lower temperature; therefore, the active methylene-type blocked isocyanate causes the coating film to cure by the crosslinking reaction progressing at lower temperature.
As the active methylene-type blocking agent, for example, dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, acetylacetone, etc. can be used.
Usually, the isocyanate compound is configured from a monomer, dimer and trimer. The main components of the isocyanate compound are the dimer uretodione structure and trimer isocyanurate structure, and these account for about 99.5% thereof. The monomer constituting the remaining about 0.5% is said to have high toxicity to organisms; however, according to a blocked isocyanate in which the isocyanate group is blocked by a blocking agent, the high toxicity thereof is avoided.
The curing catalyst is configured to contain a melamine curing catalyst and a blocked isocyanate curing catalyst.
As the melamine curing catalyst, strong acid catalysts such as an organic sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid and p-toluene sulfonic acid are used preferably.
As the blocked isocyanate curing catalyst, dibutyltin dilaurate (DBTDL), dibutyltin bis-o-phenylphenate, dibutyltin marate, dibutyltin diacetate, dibutyltin dilaurylmercaptide, dimethyltin dichloride, etc. are used preferably.
It should be noted that the melamine curing catalyst is contained in a different liquid from the liquid in which the melamine resin is contained. More specifically, in the case of the melamine resin being contained in the first liquid, the melamine curing catalyst will be contained in the second liquid. The melamine resin thereby will not react with the base resin and cure prior to coating.
With the clear coating composition according to the present embodiment, it is sufficient so long as having the melamine resin and melamine curing catalyst contained in different liquids, and each of the other components may be contained in either of the first liquid and the second liquid. For example, all components other than the melamine curing catalyst may be contained in the first liquid, and only the melamine curing catalyst contained in the second liquid.
In addition, with the clear coating composition according to the present embodiment, the mass ratio of the base resin relative to the melamine resin is set within the range of base resin/melamine resin=60/40 to 90/10=1.5 to 9.0. By blending the appropriate amount of active methylene-type blocked isocyanate as the crosslinking agent as described later, according to the mass ratio of the base resin to the melamine resin being within the range of 1.5 to 9.0, the coating film cures at lower temperature than conventionally, as well as a coating film being obtained having superior bending resistance while maintaining a constant coating film hardness.
In addition, with the clear coating composition according to the present embodiment, the minimum value for the mass percentage of the active methylene-type blocked isocyanate in the composition is calculated according to the following formula (1), and the maximum value is calculated by the following formula (2), when the total of the mass percentage of base resin and the mass percentage of melamine resin in the composition is defined as 100% by mass.
[Math. 2]
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74×(mass ratio of base resin to melamine resin)+43.21 (2)
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74×(mass ratio of base resin to melamine resin)+43.21 (2)
By the mass percentage of the active methylene-type blocked isocyanate in the composition being at least the above-mentioned minimum value, it is possible to make the coating film overall a flexible film while maintaining a certain coating film hardness due to imparting of elasticity according to the cured product of blocked isocyanate and base resin, and a coating film having superior bending resistance is obtained. On the other hand, by the mass percentage of the active methylene-type blocked isocyanate in the composition being no more than the above-mentioned maximum value, it is possible to avoid the coating film from excessively softening and the permeability increasing, and thus it is possible to avoid declines in stain resistance and acid resistance.
It should be noted that the clear coating composition according to the present embodiment is not concerned with being an aqueous system or an organic solvent system. In addition, predetermined amounts of various additives and various solvents may be contained. It is not limited in regards to production method, and can be produced according to a conventional, well-known preparation method.
Next, a method for coating an automobile body using the clear coating composition according to the present embodiment will be explained.
The method for coating an automobile body according to the present embodiment includes a base-coating coating step, a clear-coating coating step, and a curing step.
In the base-coating coating step, a base-coating film is formed by simultaneously coating the base coating on both parts among the resin part and steel sheet part of the automobile body. A conventional, well-known base coating can be used as the base coating.
In the clear-coating coating step, a clear coating film is formed by simultaneously coating a clear coating on both parts among the resin part and steel sheet part of the automobile body. The clear coating according to the present embodiment mentioned above is used as the clear coating.
In the curing step, the clear coating film is baked to cure at a predetermined temperature. For example, it can be made to cure at a low temperature of 90° C. to 120° C., and depending on the resin materials selected, it can be made to cure at a low temperature of 90° C. to 110° C. The heating time can be set to between 20 to 60 minutes, for example.
In the method for coating an automobile body according to the present embodiment, prior to the base-coating coating step, it preferably includes an electrocoating step of electrocoating steel sheet components forming the steel sheet part, and an assembly step of assembling the electrocoated steel sheet components and the resin components forming the resin part to make one set automobile body.
In this case, it is preferable for the clear coating to be coated wet-on-wet in the clear-coating coating step, and the base coating film and the clear coating film to be baked to cure simultaneously in the curing step. The effects of the clear coating composition of the present embodiment, which excels in low-temperature curability, are thereby greatly exhibited.
The method for coating according to the present embodiment is preferably applied to the so-called 4C3B coating technique. Herein, 4C3B is a coating technique of conducting intermediate-coat coating after electrocoating and electrocoat drying, then baking to cure the intermediate-coat coating film in intermediate-coat drying, followed by sequentially coating the base coating film and clear coating film wet-on-wet and simultaneously baking to cure.
In this 4C3B, the resin components are preferably applied a conductive primer, and then inserted in the step after the intermediate-coat drying of the steel sheet components. After insertion, the resin components and steel sheet components are assembled to make the automobile body, and then the base coating film and the clear coating film are sequentially coated wet-on-wet, followed by simultaneously baking to cure. In this case, the base coating film may be a configuration of two or more layers.
In addition, the method for coating according to the present embodiment can also be applied to the so-called 4C2B coating technique. Herein, 4C2B is a coating technique in which the intermediate-coat drying step of the aforementioned 4C3B is omitted from the viewpoint of a reduction in CO2 emissions.
In this 4C2B, the resin components are preferably applied a conductive primer, and then inserted in the step after the electrocoat drying of the steel sheet components. After insertion, the resin components and steel sheet components are assembled to make the automobile body, and then the base coating film and the clear coating film are sequentially coated wet-on-wet, followed by simultaneously baking to cure. However, the resin components are inserted in the step after intermediate-coat preheating of the steel sheet components, and intermediate-coat coating does not need to be performed for the resin components.
In addition, the method for coating according to the present embodiment can also be applied to the so-called 3C2B coating technique. Herein, 3C2B is a coating technique in which the intermediate-coat coating step of the aforementioned 4C2B is omitted, and the base coating film is made a two-layer configuration from the viewpoint of a reduction in CO2 emissions.
In this 3C2B, the resin components are preferably applied a conductive primer, and then inserted in the step after the electrocoat drying of the steel sheet components. After insertion, the resin components and steel sheet components are assembled to make the automobile body, and then the base coating film (two-layer configuration) and the clear coating film are sequentially coated wet-on-wet, followed by simultaneously baking to cure.
In any of the aforementioned coating techniques, the top coat coating step of resin components such as bumpers, which has conventionally been performed separately, becomes unnecessary as stated above.
It should be noted that, in any of the aforementioned coating techniques, a predetermined pretreatment step is preferably included prior to the electrocoating of steel sheet components. In addition, auxiliary material step to apply sealers such as a dust sealer, soundproofing undercoat and a melting sheet, and a chipping primer coating step may be included after the electrocoat drying of the steel sheet components. Regarding the chipping primer, it may be consolidated with the conductive primer.
According to the present embodiment, the following effects are exerted.
In the present embodiment, the clear coating composition is configured to contain the base resin containing acrylic polyol, the crosslinking agent consisting of active methylene-type blocked isocyanate and melamine resin, and the curing catalyst. In addition, the mass ratio of the base resin relative to the melamine resin is set to within the range of 1.5 to 9.0.
According to the present embodiment, by blending an active methylene-type blocked isocyanate having a property of curing at low temperature, in addition to the melamine resin, it is possible to bake to cure at a lower temperature than conventionally, e.g., a low temperature of 90° C. to 120° C. For this reason, for example, even without using heat resistant resin components (e.g., resin components blending glass filler), simultaneous coating is possible on both parts among the resin part and the steel sheet part of an automobile body, and thus it is possible to avoid deviation in hue occurring when coating each respective part.
In addition, with the present embodiment, the minimum value for the mass percentage of the active methylene-type blocked isocyanate in the composition is defined as a value calculated according to the aforementioned formula (1), and the maximum value is defined as a value calculated according to the aforementioned formula (2), when the total of the mass percentage of the base resin and the mass percentage of the melamine resin in the composition is defined as 100% by mass.
Herein, the cured product has a hard characteristic due to the melamine resin and base resin; whereas, the cured product of the blocked isocyanate and base resin has a soft characteristic. Therefore, according to the present embodiment, it is possible to appropriately control the elasticity of the coating film, by setting the mass percentage of the active methylene-type blocked isocyanate in the composition to within a specific range. More specifically, by defining the mass percentage of the active methylene-type blocked isocyanate in the composition as at least the above-mentioned minimum value, it is possible to make the coating film overall a flexible film while maintaining a fixed coating film hardness due to imparting of elasticity according to the cured product of blocked isocyanate and base resin, and a coating film having superior bending resistance is obtained. On the other hand, by defining the mass percentage of the active methylene-type blocked isocyanate in the composition as no more than the above-mentioned maximum value, it is possible to avoid the coating film from excessively softening and the permeability increasing, and thus it is possible to avoid declines in stain resistance and acid resistance.
In addition, in the present embodiment, the curing catalyst is configured to include dibutyltin dilaurate as the blocked isocyanate curing catalyst, and p-toluene sulfonic acid as the melamine curing catalyst.
It is thereby possible to cause the crosslinking reaction by the blocked isocyanate and the crosslinking reaction by the melamine resin to reliably progress, respectively, and more reliably cause the coating film to cure.
In addition, in the present embodiment, the curing catalyst is configured to include a melamine curing catalyst. In addition, the clear coating composition is made as two-part type, with the melamine resin being contained in the first liquid, while the melamine curing catalyst is contained in the second liquid.
It is thereby possible to avoid the melamine resin having a characteristic of the crosslinking reaction progressing at low temperature from reacting with the base resin and curing prior to mixing the first liquid and second liquid, and then coating. In other words, a coating composition is obtained that excels in low-temperature curability during coating, while excelling in production engineerability.
In addition, in the present embodiment, the aforementioned clear coating composition is used in a method for coating that simultaneously coats a base coating on both parts among resin part and steel sheet part of an automobile body, and then simultaneously coating a clear coating and allowing to cure. The same effects as the invention of the aforementioned clear coating composition are thereby exerted.
In addition, in the present embodiment, the resin components are assembled to the electrocoated steel sheet components to construct the automobile body, and the base coating is coated on this. Moreover, subsequently, the clear coating is coated wet-on-wet, and the base coating film and clear coating film are simultaneously baked to cure.
Normally, the coating film formed by wet-on-wet coating has a characteristic of being difficult to cure; however, since the clear coating composition according to the present embodiment excels in low-temperature curability, it is possible to cause the coating film to reliably cure even under low-temperature conditions, and thus a coating film can be formed that excels in bending resistance, stain resistance and acid resistance. In other words, the clear coating composition according to the present embodiment is suited to wet-on-wet coating.
It should be noted that the present invention is not to be limited to the above-mentioned embodiment, and that modifications, improvements, etc. within a scope that can achieve the object of the present invention are included in the present invention.
Next, the present invention will be explained in further detail based on examples; however, the present invention is not to be limited to these.
(Preparation of Clear Coating Composition)
Using an acrylic polyol having an OHV (hydroxyl value) of 150 KOH mg/g, hexamethoxy methylated melamine resin “CYMEL (registered trademark) 300” manufactured by Nihon Cytec Industries Inc., active methylene-type blocked isocyanate “Duranate (registered trademark) MF-K60X” manufactured by Asahi Kasei Chemicals Corp. in which 1,6-hexamethylene diisocyanate is blocked by an active methylene compound, the respective components were blended at the proportions shown in Table 1, thereby preparing the respective clear coating compositions of Examples 1 to 15 and Comparative Examples 1 to 4.
(Coating)
Coating was conducted separately on the bumpers of resin components and the body of steel sheet components. However, the coating conditions and curing conditions of the base coating composition and the coating conditions and curing conditions of the clear coating composition were the same for the bumpers and body.
(Bumper)
The surface of a polypropylene material for bumpers was cleaned in advance with tap water, and then a conductive primer “RB-116” manufactured by Nippon Bee Chemical Co., Ltd. was applied to form a conductive primer coating film having a film thickness of 10 μm.
Next, a base resin, in which the melamine resin and the blocked isocyanate of the crosslinking agent (both same as that blended in clear coating) were blended at the proportions shown in Table 2 to a base resin “R-301” manufactured Nippon Bee Chemical Co., Ltd., was applied to form a base coating film having a film thickness of 12 μm.
Next, each of the clear coatings of Examples 1 to 15 and Comparative Examples 1 to 4 prepared in the above way were respectively applied to form each clear coating films having a film thickness of 30 μm. After applying, the primer coating film, base coating film and clear coating film were made to cure by conducting bake drying for 20 minutes at 90° C.
(Body)
To impart rust-prevention to the body of steel sheet components, cation electrocoating was conducted. After electrocoating, an intermediate coat coating in which the melamine resin and blocked isocyanate of the crosslinking agent (both the same as that blended with clear coating) were blended at the proportions shown in Table 2 to the base resin “Polyurexcel P-1000” manufactured by Nippon Paint Co., Ltd., was applied. After applying, preheating was conducted for 5 minutes at 90° C.
Next, at the same coating conditions and curing conditions as the case of the bumpers, the base coating film and clear coating film were formed and made to cure.
The same evaluations for both the bumpers and body were conducted for the respective cured coating films of Examples 1 to 15 and Comparative Examples 1 to 4 obtained in the above way. More specifically, evaluations for the stain resistance, bending resistance and acid resistance were conducted in accordance with the below evaluation methods.
(Evaluation Methods)
(Stain Resistance)
Artificial soot was sprayed onto the cured coating films, and then left for 24 hours under a 95% humidity environment at 50° C. Next, after washing the surface of the coating film with a detergent, it was rinsed with water. A film for which a stain was confirmed visually on the cured coating film after water rinsing was judged as “X”, and a film for which no stains were confirmed was judged as “O”.
(Bending Resistance)
The cured coating film was made to bend to 90° in a state in which a steel rod with a diameter of 50 mm was pushed onto the cured coating film. At this time, a film in which cracking was confirmed in the cured coating film was judged as “X”, and a film in which no cracks were confirmed was judged as “O”.
(Acid Resistance)
Artificial acid rain was dropped onto the cured coating film, and left for 1.5 hours under a 70° C. environment. Next, the surface of the cured coating film was rinsed with a stream of water, and moisture was wiped off with a soft cloth. Subsequently, the surface roughness of the cured coating film was measured using a surface roughness gauge, and film in which etching depth was 1.0 μm or more was judged as “X”, and that less than 1.0 μm was judged as “O”.
| TABLE 1 | ||
| Comparative | ||
| Example | Example | |
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
| Acrylic | 65 | 75 | 85 | 65 | 76 | 76 | 80 | 80 | 83 | 83 | 83 | 85 | 85 | 88 | 88 | 88 | 88 | 88 | 88 |
| polyol R | |||||||||||||||||||
| (% by mass) | |||||||||||||||||||
| Melamine | 35 | 25 | 15 | 35 | 24 | 24 | 20 | 20 | 17 | 17 | 17 | 15 | 15 | 12 | 12 | 12 | 12 | 12 | 12 |
| resin MF | |||||||||||||||||||
| (% by mass) | |||||||||||||||||||
| R/MF | 1.9 | 3 | 5.7 | 1.9 | 3.2 | 3.2 | 4 | 4 | 4.9 | 4.9 | 4.9 | 5.7 | 5.7 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 |
| (mass ratio) | |||||||||||||||||||
| Blocked | 0 | 0 | 0 | 19 | 25 | 48 | 25 | 50 | 18 | 26 | 52 | 27 | 36 | 9 | 14 | 19 | 26 | 39 | 52 |
| isocyanate | |||||||||||||||||||
| BI (% by | |||||||||||||||||||
| mass) | |||||||||||||||||||
| p-toluene | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| sulfonic acid | |||||||||||||||||||
| (% by mass) | |||||||||||||||||||
| DBTDL | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| (% by mass) | |||||||||||||||||||
| Stain | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ |
| resistance | |||||||||||||||||||
| Bending | X | X | X | X | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ |
| resistance | |||||||||||||||||||
| Acid | X | X | X | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ | ◯ |
| resistance | |||||||||||||||||||
| TABLE 2 | |||
| Intermediate | |||
| coat coating | Base coating | ||
| Base resin Polyurexcel P-1000 (% by mass) | 85 | — |
| Base resin R-301 (% by mass) | — | 85 |
| Melamine resin MF (% by mass) | 15 | 15 |
| Blocked isocyanate BI (% by mass) | 27 | 27 |
| p-toluene sulfonic acid (% by mass) | 1 | 1 |
| DBTDL (% by mass) | 0.1 | 0.1 |
The evaluation results are as shown in Table 1. It should be noted that, since the evaluation results were the same for the body and bumper for each of the respective Examples and respective Comparative Examples, they are shown as common evaluation results of the body and bumper.
As shown in Table 1, the cured coating films of Comparative Examples 1 to 4 were all found to have evaluations for bending resistance or acid resistance of X. In contrast, the cured coating films of Examples 1 to 15 were confirmed to have evaluations for all of stain resistance, bending resistance and acid resistance of “O”, despite having been cured at a low temperature of 90° C.
Herein, the relationships of the respective contents of acrylic polyol, melamine resin and active methylene-type blocked isocyanate in the clear coating compositions of Examples 1 to 15 for which the evaluation results for stain resistance, bending resistance and acid resistance were all “O” will be considered while referencing FIG. 1 .
As shown in FIG. 1 , the minimum value and maximum value for the mass percentage of active methylene-type blocked isocyanate in the composition when defining the total of the mass percentage of acrylic polyol and the mass percentage of melamine resin in the composition as 100% by mass are respectively found to be in a fixed linear relationship with the mass ratio of the acrylic polyol relative to the melamine resin (hereinafter referred to as “R/MF”).
More specifically, a certain relationship between the minimum value and R/MF is represented by a minimum line defined by y=−4.13×+38.52, which was calculated according to the least-squares method using the data of Examples 1, 3, 5 and 10.
In addition, a certain relationship between the maximum value and R/MF is represented by a maximum line defined by y=1.74×+43.21 calculated according to the least-squares method using the data of Examples 2, 4, 7 and 15.
From the above results, it was confirmed that a certain minimum value is calculated according to the aforementioned formula (1), and a certain maximum value is calculated according to the aforementioned formula (2).
In addition, when calculating the minimum value according to the above-mentioned formula using the value of R/MF of Comparative Example 4, it was calculated as about 31% by mass. In contrast, since the mass percentage of the active methylene-type blocked isocyanate in the composition when defining the total of the mass percentage of acrylic polyol and the mass percentage of melamine resin in the composition of Comparative Example 4 as 100% by mass was 19% (refer to Table 1), it was confirmed that Comparative Example 4 greatly falls below the minimum value.
Claims (4)
1. A method for coating an automobile body, comprising:
a base-coating coating step of simultaneously coating a base coating on both parts among a resin part and a steel sheet part of an automobile body to form a base coating film thereon;
a clear-coating coating step of simultaneously coating a clear coating on both parts among the resin part and the steel sheet part on which the base coating film was formed to form a clear coating film thereon; and
a curing step of baking the dear coating film to cure,
wherein the clear-coating coating step coats a clear coating composition that comprises:
a base resin containing acrylic polyol;
a crosslinking agent consisting of an active methylene blocked isocyanate and melamine resin; and
a curing catalyst that contains dibutyltin dilaurate as a blocked isocyanate curing catalyst, and p-toluene sulfonic acid as a melamine curing catalyst,
wherein a mass ratio of the base resin to the melamine resin is 1.5 to 9.0,
when defining a total of mass percentage of the base resin and mass percentage of the melamine resin in the composition as 100% by mass, the minimum value for mass percentage of the active methylene blocked isocyanate in the composition is calculated according to formula (1) below, and the maximum value thereof is calculated according to formula (2) below, and
wherein the base-coating coating step coats a base coating that contains the active methylene blocked isocyanate and the melamine resin, which are the same as those blended in the clear coating composition,
[Math. 1]
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74×(mass ratio of base resin to melamine resin)+43.21 (2).
Minimum value=−4.13×(mass ratio of base resin to melamine resin)+38.52 (1)
Maximum value=1.74×(mass ratio of base resin to melamine resin)+43.21 (2).
2. A method for coating an automobile body according to claim 1 ,
wherein the clear coating composition is a two-part coating composition consisting of a first liquid and a second liquid,
the melamine resin being contained in the first liquid, and the melamine curing catalyst being contained in the second liquid.
3. A method for coating an automobile body according to claim 1 , further comprising:
an electrocoating step of electrocoating a steel sheet component forming the steel sheet part, prior to the base-coating coating step; and
an assembly step of assembling the steel sheet component thus electrocoated and a resin component forming the resin part so as to make a set of an automobile body,
wherein the clear coating is coated wet-on-wet in the clear-coating coating step, and
wherein the base coating film and the clear coating film are simultaneously baked to cure in the curing step.
4. A method for coating an automobile body according to claim 2 , further comprising:
an electrocoating step of electrocoating a steel sheet component forming the steel sheet part, prior to the base-coating coating step; and
an assembly step of assembling the steel sheet component thus electrocoated and a resin component forming the resin part so as to make a set of an automobile body,
wherein the clear coating is coated wet-on-wet in the clear-coating coating step, and
wherein the base coating film and the clear coating film are simultaneously baked to cure in the curing step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011153977 | 2011-07-12 | ||
| JP2011-153977 | 2011-07-12 | ||
| PCT/JP2012/067793 WO2013008879A1 (en) | 2011-07-12 | 2012-07-12 | Clear coating composition and method for coating automobile body |
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| Publication Number | Publication Date |
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| US20140147597A1 US20140147597A1 (en) | 2014-05-29 |
| US9533328B2 true US9533328B2 (en) | 2017-01-03 |
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| US14/130,455 Active 2033-07-26 US9533328B2 (en) | 2011-07-12 | 2012-07-12 | Clear coating composition and method for coating automobile body |
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| US (1) | US9533328B2 (en) |
| EP (1) | EP2719733B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019204095A1 (en) | 2018-04-20 | 2019-10-24 | Carbon, Inc. | Bonded surface coating methods for additively manufactured products |
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| JP6138323B1 (en) * | 2016-07-13 | 2017-05-31 | 関西ペイント株式会社 | Multi-layer coating formation method |
| US10113085B2 (en) * | 2016-07-26 | 2018-10-30 | Basf Coatings Gmbh | Low temperature cure coating formed via a double layer curing mechanism of a pigmented waterborne baselayer and a solventborne top layer |
| US10208230B2 (en) * | 2016-07-26 | 2019-02-19 | Basf Coatings Gmbh | One component, low temperature cure coating formed via a double layer curing mechanism |
| ES2901878T3 (en) * | 2017-07-26 | 2022-03-24 | Basf Coatings Gmbh | Low-temperature curing coating formed through interlayer polarity-facilitated migration of catalyst in a dual-layer curing mechanism |
| US11541420B2 (en) | 2018-05-09 | 2023-01-03 | Kansai Paint Co., Ltd. | Method for forming multilayer coated film |
| KR102567440B1 (en) * | 2021-03-30 | 2023-08-16 | 주식회사 케이씨씨 | Single-liquid type clear coat composition for low temperature curing |
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| WO2019204095A1 (en) | 2018-04-20 | 2019-10-24 | Carbon, Inc. | Bonded surface coating methods for additively manufactured products |
| US11207835B2 (en) | 2018-04-20 | 2021-12-28 | Carbon, Inc. | Bonded surface coating methods for additively manufactured products |
| US11813795B2 (en) | 2018-04-20 | 2023-11-14 | Carbon, Inc. | Bonded surface coating methods for additively manufactured products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103635548A (en) | 2014-03-12 |
| WO2013008879A1 (en) | 2013-01-17 |
| US20140147597A1 (en) | 2014-05-29 |
| JP5766802B2 (en) | 2015-08-19 |
| JPWO2013008879A1 (en) | 2015-02-23 |
| EP2719733B1 (en) | 2016-03-16 |
| EP2719733A4 (en) | 2014-12-31 |
| EP2719733A1 (en) | 2014-04-16 |
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